Phase change ink formulation using urethane isocyanate-derived resins and a polyethylene wax

ABSTRACT

Urethane resins are made by reacting selected nucleophiles, including alcohols, with an isocyanate. The order of addition of the isocyanate and the different nucleophiles can tailor the distribution of di-urethane and mixed urethane/urea molecules in the final resin product. The isocyanate-derived resin materials are useful as ingredients as phase change ink carrier compositions used to make phase change ink jet inks.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 08/672,815 filed on Jun. 28, 1996 now issued asU.S. Pat. No. 5,830,942, and U.S. patent application Ser. No. 09/013,410filed on Jan. 26, 1998 which applications are specifically incorporatedherein by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to phase change inks. Moreparticularly, the present invention relates to a phase change carriercomposition containing the combination of a plurality of urethaneresins, at least one amide wax, and at least one polyethylene wax.Additionally, the present invention relates to inks useful for printingapplications formed by adding colorant materials to such carriercompositions. Still further, the present invention relates to processesof using these phase change ink compositions containing such phasechange inks in a printing device. The phase change inks possess improveddocument feed capability when used to create images on paper that isused in a photocopier.

2. Description of the Relevant Art

In general, phase change inks (sometimes referred to as "hot melt inks")are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the printing media, they quickly solidify to form apredetermined pattern of solidified ink drops. Phase change inks havealso been investigated for use in other printing technologies such asgravure printing as referenced in U.S. Pat. No. 5,496,879 and Germanpatent publications DE 4205636AL and DE 4205713AL assigned to SiegwerkFarbenfabrik Keller, Dr. Rung and Co.

Phase change inks for color printing generally comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. Preferably, a colored phase change ink will beformed by combining the above-described ink carrier composition withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks of this invention can comprise four componentdyes, namely, cyan, magenta, yellow and black. U.S. Pat. Nos. 4,889,506;4,889,761; and 5,372,852 teach that the subtractive primary colorantsemployed typically may comprise dyes from the classes of Color Index(C.I.) Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, and alimited number of Basic Dyes. The colorants can also include pigments asexemplified in U.S. Pat. No. 5,221,335, assigned to CoatesElectrographics LTD. U.S. patent application Ser. No. 08/381,610, filedJan. 30, 1995, and assigned to Tektronix, Inc., is directed to the useof a specific class of polymeric dyes in phase change ink compositions.

Phase change inks are desirable for ink jet printers since they remainin a solid phase at room temperature during shipping, long-term storage,and the like. Also, the problems associated with nozzle clogging due toink evaporation are largely eliminated, thereby improving thereliability of ink jet printing. Furthermore, in the above-noted priorart phase change ink jet printers where the ink droplets are applieddirectly onto the printing medium the droplets solidify immediately uponcontact with the substrate, migration of ink along the printing mediumis prevented and dot quality is improved. This is also true of theprocesses and ink compositions described herein.

In addition to the above-referenced U.S. patents, many other patentsdescribe materials for use in phase change ink jet inks. Somerepresentative examples include U.S. Pat. Nos. 3,653,932; 4,390,369;4,484,948; 4,684,956; 4,851,045; 4,889,560; 5,006,170; and 5,151,120; aswell as EP Application Nos. 0187352 and 0206286. These materials caninclude paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide-containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters are an example) andmany synthetic resins, oligomers, polymers and co-polymers.

Separately, PCT Patent Application WO 94/14902, which was published onJul. 7, 1994 and is assigned to Coates Brothers PLC, teaches a hot meltink containing a colorant and, as a vehicle for the hot melt ink, anoligourethane having a melting point of at least 65° C. and obtained byreacting an aliphatic or aromatic diisocyanate with at least astoichiometric amount of either: (i) a monohydric alcohol component; or(ii) a monohydric alcohol component followed by another differentmonohydric alcohol component; or (iii) a monohydric alcohol component,followed by a dihydric alcohol component, followed by a monohydricalcohol component.

This PCT patent application defines the monohydric alcohol component aseither a monohydric aliphatic alcohol (e.g. C₁ to C₂₂ alcohols), anetherified dihydric aliphatic alcohol (e.g. propylene glycol methylether (PGME), dipropylene glycol methyl ether (DPGME), ethylene glycolbutyl ether (EGBE), diethylene glycol butyl ether (DPGBE), tripropyleneglycol butyl ether (TPGBE) and propylene glycol phenyl ether (PPL));esterified dihydric aliphatic alcohol (e.g. the esterifing acid may bean ethylenically unsaturated acid (such as acrylic acid or methacrylicacid), thereby introducing ethylenic unsaturation into the oligourethaneand rendering it suitable for eventual further additional polymerization(curing) after having been applied to a substrate by hot melt printing),or dihydric polyalkylene glycol. This PCT Application further definedthe dihydric alcohol component as a dihydric aliphatic alcohol or adihydric polyalkylene glycol (e.g. ethylene glycol, polyethylene glycol(PEG 1500), polypropylene glycol (PPG 750, 1000 and 1500), trimethyleneglycol, dipropylene glycol, methylpropanediol and 1,6-hexanediol).

Also, PCT Patent Application WO 94/04619, assigned to the GeneralElectric Company, teaches the use of ionomeric materials in combinationwith image forming agents to form a hot melt ink jet ink. The ionomericmaterials can include many different types of copolymeric or polymericionomers, including carboxyl-functional polyurethanes prepared from adiol or polyol and a hydroxyl acid. Many other carrier materials andcolorants for the image forming agent of the invention are included inthis PCT application.

There is still a need for new materials for novel and differentapplications of phase change carrier compositions and phase change inkscontaining these carrier compositions. There is also a need forrelatively low viscosity resins, including non-polymeric resins, andwaxes designed for phase change ink jet and other forms of phase changeink printing. Additionally, needs continue to exist for phase changeinks which can be used to create imaged output that can be reliably andeasily be fed automatically through photocopiers. These needs are solvedby the present invention by providing a means to tailor the propertiesof these resin materials for specific applications.

BRIEF SUMMARY OF THE INVENTION

It is an aspect of the present invention that urethane compoundscomprising the reaction product of selected isocyanates with selectedalcohols or mixtures of selected alcohols are obtained.

It is another aspect of the present invention that phase change inkcompositions are made from the admixture of at least one urethane resin;at least one polyethylene wax and a phase change compatible colorant.

It is still another aspect of the present invention that coloredurethane compounds comprising the reaction product of selectedisocyanates with mixtures of selected alcohols or mixtures of selectedalcohols and chromogen-containing nucleophiles are obtained.

It is yet another aspect of the present invention that a method forproducing a layer of a phase change colored ink on the surface of asubstrate by either direct or indirect printing is obtained wherein thephase change ink composition in the solid phase comprises an admixtureof (a) a phase change carrier composition containing at least oneisocyanate-derived resin, (b) at least one polyethylene wax, and (b) aphase change ink compatible colorant.

It is a feature of the present invention that the at least one alcoholused to react with the isocyanate is a straight chained monohydricaliphatic alcohol of carbon chain length 20 or higher.

It is a feature of the present invention that the phase change inkcarrier composition and the phase change ink obtained from such carriercomposition possesses a low viscosity in the liquid phase and a lowcoefficient of friction against glass in the solid phase.

It is an advantage of the present invention that the isocyanate-derivedresins or waxes can be design engineered to obtain desired propertiesfor specific printing platforms and architectures.

It is another advantage of the present invention that theisocyanate-derived resins or waxes are very pure, being free of saltsand other insoluble contaminants.

These and other aspects, features and advantages are obtained by the useof reaction products of selected isocyanates with selected alcohols,mixed with amide and polyethylene waxes in phase change inks to producephase change inks having low coefficients of friction that may beemployed in direct or indirect printing applications.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "nucleophile" in the present specification and claims is usedas defined on page 179 of "Advanced Organic Chemistry", 3rd Edition byJerry March, ©1985 by John Wiley and Sons, to describe a reagent thatbrings an electron pair to a reaction to form a new bond. The preferrednucleophiles of this invention are alcohols or amines, but it isunderstood that other nucleophilic functional groups that are capable ofreacting with the isocyanate moiety could also be used in the invention.

The term "oligomer" in the current specification and claims is used asdefined on page 7 of "Polymer Chemistry--The Basic Concepts" by PaulHiemenz, ©1984 by Marcel Dekker, Inc., to describe a term coined todesignate molecules for which n (representing the number of repeatingmonomer units) is less than 10.

The term "isocyanate-derived resin" as used in the present specificationand claims is defined as any monomeric, oligomeric or non-polymericresinous material derived from the reaction of mono-, di-, orpoly-isocyanates with suitable nucleophilic molecules.

The term "isocyanate-derived wax" as used in the present specificationand claims is defined as any crystalline or semicrystalline waxymaterial derived from the reaction of a fatty isocyanate with a suitablenucleophile, or the reaction of a fatty nucleophile with a suitableisocyanate, or the reaction of a fatty nucleophile with a fattyisocyanate.

The term "urethane resin" or "urethane isocyanate-derived resin" as usedin the present specification and claims is defined as any resin that isa urethane that is the product of the reaction of an isocycanate and analcohol.

The term "mixed urethane/urea resin" or "urethane/ureaisocyanate-derived resin" as used in the present specification andclaims is defined as any resin that is a mixed urethane/urea that is theproduct of the reaction of an isocycanate, an alcohol and an amine.

Any suitable reaction condition for making urethane or mixedurethane/urea compounds by condensing alcohols and/or amines withisocyanates may be employed in the practice of the present invention.Preferably, the reaction is carried out at elevated temperatures (e.g.about 60° C. to about 160° C.) in the presence of a urethane reactioncatalyst such as dibutyltindilaurate, bismuth tris-neodecanoate, cobaltbenzoate, lithium acetate, stannous octoate or triethylamine. Thereaction conditions preferably are conducted in an inert atmosphere,such as argon or nitrogen gas or other suitable atmosphere, to preventoxidizing or yellowing the reaction products and to prevent undesirableside reactions. The mole ratio of reactants is adjusted so that theisocyanate functionalities are completely consumed in the reaction witha slight molar excess of alcohol or amine typically remaining.Conceptually the reactants can be added together in any order and/oradded to the reaction as physical mixtures. However, in the preferredembodiments of the invention, reaction conditions and the order of theaddition of reactants are carefully controlled for several reasons.First, reaction conditions and reactant additions are chosen to providea controlled exothermic reaction. Secondly, when reacting mixtures ofalcohols and/or amines with diisocyanates such as isophoronediusocyanate (IPDI), the order of addition of the isocyanate and thedifferent nucleophiles to the reaction is chosen to tailor thedistribution of diurethane molecules, and/or mixed urethane/ureamolecules, and/or diurea molecules in the final resin. When doing this,the different reactivities to isocyanates of alcohols versus amines areemployed, as are the different reactivities of the two separateisocyanate groups on IPDI. See J. H. Saunders and K. C. Frisch's"Polyurethanes Part I, Chemistry" published by Interscience of New York,N.Y. in 1962 and Olin Chemicals' Luxateg® IM isophorone diisocyanatetechnical product information sheet which provide further explanation ofthis chemistry. This control of the reaction conditions and order ofaddition of the reactants is done to specifically tailor or customizethe different types of molecular species in the finished resin so thatthe resin will:

(1) have a controlled viscosity that is designed for a specificapplication,

(2) have a controlled glass transition temperature and/or melting point,and

(3) have consistent properties from batch to batch.

The isocyanate-derived resins from these reactions are generallytransparent solids having melting points in the range of about 20° C. toabout 150° C., viscosities in the range of about 10 cPs to about 5000cPs at 150° C. and T_(g) 's of about -30° C. to about 100° C. Theisocyanate-derived waxes from these reactions are generally opaque waxysolids having sharp melting points from about 50° C. to about 130° C.,and viscosities of about 1 cPs to about 25 cPs at 140° C. Theisocyanate-derived resins and waxes display properties such that thehigher the T_(g) and the melting point, the higher is the viscosity.While the structural activity relationships are not fully understood, itis known that the T_(g) of the isocyanate-derived resins is controlledby the proper choice of the mixture of nucleophiles in the reaction asillustrated in Table 3 in the aforementioned incorporated by referenceU.S. application Ser. No. 08/672,815. Varying one or more of the readilyavailable commodity chemicals used as chemical precursors will permitcustom-tailoring of the properties of the isocyanate-derived resin andwax materials.

Preferred alcohols to react with difunctional and higher isocyanates tomake the isocyanate-derived waxes and resins of this invention includeany monohydric alcohol. For instance, the monohydric alcohol could beany aliphatic alcohol [e.g., a C₁ -C₂₂ or higher linear alcohol, anybranched alcohol or any cyclic aliphatic alcohol such as methanol,ethanol, (n- and iso)-propanol, (n-, iso-, t-) butanol, (n-, iso-, t-,and the like) pentanol, (n-, iso-, t-, and the like) hexanol, (n-, iso-,t-, and the like) octanol, (n-, iso-, t-, and the like) nonanol, (n- andbranched) decanols, (n- and branched) undecanols, (n- and branched)dodecanols, (n- and branched) hexadecanols, (n- and branched)octadecanols, 3-cyclohexyl- 1-propanol, 2-cyclohexyl- 1-ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like]; analiphatic/aromatic alcohol [e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates of octyl, nonyl, and dodecylphenol, andalkoxyphenol]; aromatic alcohols such as phenol, naphthol, and the like,and their derivatives; fused ring alcohols (e.g., rosin alcohols,hydroabietyl alcohol, cholesterol, vitamin E, and the like) and othersuitable alcohols (e.g., N,N-dimethyl-N-ethanolamine,stearamide-monoethanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like). It will be obvious to those skilled in theart that small amounts (on a molar basis) of polyols could also beincorporated into the reaction mixture to produce oligomeric species inthe resins if so desired. The preferred alcohols are hydroabietylalcohol, octylphenol ethoxylate and octadecyl alcohol.

The most preferred alcohol to use to react with an isocyanate to createan urethane resin that can be incorporated into a low coefficient offriction phase change ink is a straight chained monohydric aliphaticalcohol of carbon chain length 20 or higher.

Preferred amines to react with difunctional and higher isocyanates tomake the isocyanate-derived waxes and resins of this invention includeany monofunctional amine, with the exception of tertiary amines void ofother nucleophilic functional groups (e.g., triethylamine). Forinstance, the monoamine could be any aliphatic primary or secondaryamine (e.g., a C₁ -C₂₂ or higher linear amine, any branched amine or anycyclic aliphatic amine) such as methyl amine, ethyl amine, (n- andiso-)propyl amine, (n-, iso-, and t-) butyl amine, (n-, iso-, t-, andthe like) pentyl amine, (n-, iso-, t-, and the like) hexyl amine, (n-,iso-,t-, and the like) octyl amine, (n-, iso-, t-, and the like) nonylamine, (n- and branched) decyl amine, (n- and branched) undecyl amines,(n- and branched) dodecyl amines, (n- and branched) hexadecyl amines,(n- and branched) dodecyl amines, dimethyl amine, diethyl amine, di(n-and iso-)propyl amines, di(n-, iso-, t-)butyl amine, di(n-, iso-, t-,and the like)pentyl amine, di(n-, iso-, t-, and the like)hexyl amine,di(n-, iso-, t-, and the like)cyclohexyl amine, di(n-, iso-, t-, and thelike)heptyl amine, di(n-, iso-, t-, and the like)octyl amine, di(n-,iso-, t-, and the like)decyl amine, di(n-, iso-, t-, and thelike)dodecyl amine, di(n-, iso-, t-, and the like)octadecyl amine,cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine, piperidine,pyrrolidine, and the like; an aliphatic/aromatic amine (e.g., benzylamine or analogues with longer or additional alkyl chains); aromaticamines such as aniline, anisidine, and the like; fused ring amines suchas rosin amine, dehydroabietyl amine, dihydroabietyl amine, hydroabietylamine, and the like; and miscellaneous amines (e.g., adamantyl amine,isonipecotamide, polyoxyalkylenemonoamines, such as M-series Jeffaminesavailable commercially from Huntsman Chemical Company of Austin, Tex.;3,3'-diamino-N-methyl-dipropylamine, and the like. It will be obvious tothose skilled in the art that small amounts (on a molar basis) ofpolyamines could also be incorporated into the reaction mixture toproduce oligomeric species in the resins if so desired. The preferredamine is octadecyl amine.

Preferred alcohols to react with monofunctional isocyanates to make theisocyanate-derived waxes and resins of this invention include anymonohydric alcohol. For instance, the monohydric alcohol could be anyaliphatic alcohol [e.g., a C₁ -C₂₂ or higher linear alcohol, anybranched alcohol or any cyclic aliphatic alcohol such as methanol,ethanol, (n- and iso-)propanol, (n-, iso-, and t-) butanol, (n-, iso-,t-, and the like) pentanol, (n-, iso-, t-, and the like) hexanol, (n-,iso-, t-, and the like) octanol, (n-, iso-, t-, and the like) nonanol,(n- and branched) decanols, (n- and branched) undecanols, (n- andbranched) dodecanols, (n- and branched) hexadecanols, (n- and branched)octadecanols, 3-cyclohexyl-1-propanol, 2-cyclohexyl-1-ethanol,cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like]; analiphatic/aromatic alcohol (e.g., benzyl alcohol, octyl, nonyl, anddodecylphenol alkoxylates or octyl, nonyl, and dodecylphenol,alkoxyphenol); aromatic alcohols such as phenol, naphthol, and the like,and their derivatives; fused ring alcohols (e.g., rosin alcohols,hydroabietyl alcohol, cholesterol, vitamin E, and the like) and othersuitable alcohols (e.g., N,N-dimethyl-N-ethanolamine,stearamide-monoetbanolamine, tripropyleneglycol monomethylether,hydroxybutanone, menthol, isoborneol, terpineol, 12-hydroxy stearylstearamide, and the like), as well as multifunctional alcohols such asethylene glycol, diethylene glycol, triethylene glycol,dimethylolpropionic acid, sucrose, polytetramethylene glycol (MW<˜3000),polypropylene glycol (MW<˜3000), polyester polyols (MW<˜3000),polyethylene glycol (NMW<˜3000), pentaerythritol, triethanol amine,glycerin, 1,6-hexanediol, N-methyl-N,N-diethanol amine, trimethylolpropane, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and thelike. The preferred alcohol is octadecanol.

Preferred amines to react with monofunctional isocyanates to make theisocyanate-derived waxes and resins of this invention include anymonofunctional amine, with the exception of tertiary amines void ofother nucleophilic functional groups (e.g., triethylamine). Forinstance, the monoamine could be any aliphatic primary or secondaryamine [e.g., a C₁ -C₂₂ or higher linear amine, any branched amine or anycyclic aliphatic amine such as methyl amine, ethyl amine, (n- andiso-)propyl amine, (n-, iso-, and t-) butyl amine, (n-, iso-, t-, andthe like) pentyl amine, (n-, iso-, t-, and the like) hexyl amine, (n-,iso-, t-, and the like) octyl amine, (n-, iso-, t-, and the like) nonylamine, (n- and branched) decyl amine, (n- and branched) undecyl amine,(n- and branched) octadecyl amine, (n- and branched) hexadecyl amine,(n- and branched) dodecyl amine, dimethyl amine, diethyl amine, di(n-,and iso-)propyl amine, di(n-, iso-, t-)butyl amine, di(n-, iso-, t-, andthe like)pentyl amine, di(n-, iso-, t-, and the like)hexyl amine, di(n-,iso-, t-, and the like)cyclohexyl amine, di(n-, iso-, t-, and thelike)heptyl amine, di(n-, iso-, t-, and the like)coctyl amine, di(n-,iso-, t-, and the like)decyl amine, di(n-, iso-, t-, and thelike)octadecyl amine, di(n-, iso-, t-, and the like)dodecyl amine,cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine, piperidine,pyrrolidine, and the like]; any aliphatic/aromatic amines (e.g., benzylamine or analogues with longer or additional alkyl chains); aromaticamines such as aniline, anisidine, and the like; fused ring amines suchas rosin amine, dehydroabietyl amine, dihydroabietyl amine, hydroabietylamine, and the like; and miscellaneous amines (e.g., adamantyl amine,isonipecotamide, polyoxyalkylenemono-, di-, or triamines, such as M-,D-, and T-series Jeffamines available commercially from HuntsmanChemical Company of Austin, Tex.; 3,3'-diamino-N-methyl-dipropylamine,and the like, as well as multifunctional amines such as polyethyleneimine; ethylene diamine; hexamethylene diamine; isomers ofcyclohexyldiamines; 1,3-pentadiamine; 1,12-dodecanediamine;3-dimethylaminopropylamine; 4,7,10-trioxa-1,13-tridecanediamine;diethylene triamine; 3,3-diamino-N-methyldipropylamine;tris(2-aminoethyl)amine, and the like. The preferred amine isoctadecylamine.

Additionally, hydroxyl/amino containing compounds can be employed (withdi- and higher functionality isocyanates taking advantage of thedifference in reactivity of the amine over the hydroxyl group, or withmonoisocyanates reacting with the amine preferentially or with both theamine and the hydroxyl groups). Examples of this include ethanolamine,diethanolamine, and the like.

Additionally amides or other nucleophile containing compounds can bereacted with the isocyanates (mono, di, and the like). Some examplesinclude: urea, oleamide, stearamide, or the like.

Preferred precursors to the isocyanate-derived resins and waxes of thepresent invention include mono-, di- and other poly-isocyanates.Examples of monoisocyanates include octadecylisocyanate;octylisocyanate; butyl and t-butylisocyanate; cyclohexyl isocyanate;adamantyl isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropylisocyanate; benzylisocyanate; 2-ethylphenylisocyanate;benzoylisocyanate; meta and paratolylisocyanate; 2-, 3-, or4-nitrophenylisocyanates; 2-ethoxyphenyl isocyanate; 3-methoxyphenylisocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;2,6-dimethylphenylisocyante; 1-naphthylisocyanate;(naphthyl)ethylisocyantes; and the like. Examples of diisocyanatesinclude isophorone diisocyanate (IPDI); toluene diisocyanate (TDI);diphenylmethane-4,4'-diisocyanate (MDI); hydrogenateddiphenylmethane-4,4'-diisocyanate (H₁₂ MDI); tetra-methyl xylenediisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;3,3'-dimethoxy-4,4'-biphenyldiisocyanate;3,3'-dimethyl-4,4'-bimethyl-4,4'-biphenyldiisocyanate; phenylenediisocyanate; 4,4'-biphenyldiisocyanate; trimethylhexamethylenediisocyanate; tetramethylene xylene diisocyanate;4,4'-methylenebis(2,6-diethylphenyl isocyanate);1,12-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;1,4-diisocyanatobutane; and cyclohexylene diisocyanate and its isomers;uretidione dimers of HDI; and the like. Examples of triisocyanates ortheir equivalents include the trimethylolpropane trimer of TDI, and thelike, isocyanurate trimers of TDI, HDI, IPDI, and the like, and biurettrimers of TDI, HDI, IPDI, and the like. Examples of higher isocyanatefunctionalities include copolymers of TDI/HDI, and the like, as well asMDI oligomers.

Phase change inks of this invention contain a phase change carriersystem or composition. The phase change carrier composition is generallydesigned for use in either a direct printing mode or use in an indirector offset printing transfer system. In the direct printing mode, thephase change carrier composition is generally made up of one or morechemicals that provide the necessary properties to allow the phasechange ink (1) to be applied in a thin film of uniform thickness on thefinal receiving substrate when cooled to the ambient temperature afterprinting directly to the substrate; (2) to be ductile while retainingsufficient flexibility so that the applied image on the substrate willnot fracture upon bending; and (3) to possess a high degree oflightness, chroma, transparency and thermal stability. In an offsetprinting transfer or indirect printing mode, the phase change carriercomposition is designed to possess not only the above mentionedproperties, but certain fluidic and mechanical properties necessary foruse in such a system, as described in U.S. Pat. No. 5,389,958 which ishereby incorporated by reference in pertinent part. The phase changecarrier composition and the inks made therefrom which collectivelycomprise the invention can contain a combination urethane resins, and/orurethane/urea resins, along with a polyethylene wax ingredient.Additionally a mono-amide ingredient can be employed in making the inks.These ingredients can be supplemented with (one or more) optionalingredients to prepare commercial phase change carrier compositions andinks. The urethane resins and the mixed urethane/urea resin materials ofthe current invention are tailored to have the desirable propertiesmentioned above when used in the carrier composition of the inks of thepresent invention by varying one or more of the readily availablecommodity chemical precursors.

The preferred chromogen-containing nucleophilic molecules include dyessuch as those disclosed in U.S. Pat. Nos. 3,994,835 and 4,132,840,assigned to Bayer, and U.S. Pat. Nos. 4,284,729; 4,507,407; 4,751,254;4,846,846; 4,912,203; 5,270,363 and 5,290,921 assigned to MillikenResearch Corporation. Also suitable may be any Color Index (C.I.)Solvent Dyes, Disperse Dyes, modified Acid and Direct Dyes, Basic Dyes,Sulphur Dyes or Vat Dyes that contain an alcohol, amine, or othernucleophilic functional group that is capable of reacting with anisocyanate. The more preferred chromogen-containing nucleophilicmolecules contain at least one alcohol functional group. Most preferablythis alcohol functional group is terminal to an alkylene oxide polymericchain, such as a butylene oxide, styrene oxide, polyethylene oxide,polypropylene oxide, or a polyethylene/polypropylene oxide polymericchain.

The phase change carrier compositions of the current invention may beused in combination with conventional phase change ink colorantmaterials such as Color Index (C.I.) Solvent Dyes, Disperse Dyes,modified Acid and Direct Dyes, Basic Dyes, Sulphur Dyes, Vat Dyes,and/or polymeric dyes such as those disclosed in U.S. Pat. No.5,621,022; and/or pigments. Alternately, the phase change carriercompositions of the current invention may employ colored urethane resinsof urethane/urea resins or other isocyanate-derived colored resins asdescribed in co-pending U.S. patent application Ser. No. 08/672,617filed Jun. 28, 1996 and assigned to the assignee of the presentinvention, now U.S. Pat. No. 5,780,528 (issued Jul. 14, 1998), toproduce a phase change ink. Where colored urethane resins are employed,they may comprise all or a portion of the colorant material.

The mono-amide ingredient of the phase change carrier compositions andthe inks made therefrom of the present invention typically compriseseither a primary or secondary mono-amide, but is preferably a secondarymono-amide. Of the primary mono-amides, stearamide, such as KEMAMIDE S,manufactured by Witco Chemical Company, can be employed herein. As forthe secondary mono-amides, behenyl benenamide (KEMAMIDE EX-666), andstearyl stearamide (KEMAMIDE S-180), both manufactured by Witco ChemicalCompany, are extremely useful mono-amides. However, stearyl stearamide(KEMAMIDE S-180) is the mono-amide of choice in producing the phasechange ink compositions of the present invention.

The other critical ingredient of the phase change carrier compositionsand the inks made therefrom of the present invention is at least onepolyethylene wax. Preferably, the polyethylene wax has a molecularweight of about 500 to about 5,000; more preferably, of about 700 toabout 2,000; and, most preferably, of about 800 to 1,200. Preferredpolyethylene waxes are Polywax 850, Polywax 1000 or Polywax 2000, allavailable from Petrolite.

Preferably, the total amount of urethane resin or resins in the phasechange carrier composition and the inks made therefrom will compriseabout 10% to about 60%, more preferably, about 15-50% and mostpreferably, about 20-50% by weight of the carrier composition.Preferably, when employed, the total amount of mixed urethane/urea resinor resins in the phase change carrier composition will likewise compriseabout 5% to about 30%, more preferably about 10-25% and most preferably,about 12-20%, by weight of the carrier composition. Preferably, thetotal amount of mono-amide wax and polyethylene wax combined willcomprise about 40% to about 70%, more preferably, about 45-60% and mostpreferably about 48-57% by weight of the carrier composition.

The ratio of mono-amide wax to the polyethylene wax is preferably fromabout 2:1 to 1:2, by weight.

Prior art phase change inks for use in direct and indirect transferprinting systems are described in U.S. Pat. Nos. 4,889,560 and5,372,852. These inks consist of a phase change ink carrier compositioncomprising one or more fatty amide-containing materials, usuallyconsisting of a mono-amide wax and a tetra-amide resin, one or moretackifiers, one or more plasticizers and one or more antioxidants, incombination with compatible colorants. A preferred tetra-arnide resin isa dimer acid based tetra-amide that is the reaction product of dimeracid, ethylene diamine, and stearic acid. A preferred mono-amide isstearyl stearamide. A preferred tackifier resin is a glycerol ester ofhydrogenated abietic (rosin) acid and a preferred antioxidant is thatprovided by Uniroyal Chemical Company under the tradename Naugard 524.The isocyanate-derived resins and/or isocyanate-derived waxes of thepresent invention can replace one or more of the ingredients in theabove phase change ink carrier composition or the inks of the presentinvention can have all of the above ingredients replaced by theisocyanate-derived resins and/or waxes of the present invention. Theadvantages of inks formulated with isocyanate-derived resins and/orisocyanate-derived waxes over the prior art phase change inks are:

(1) The urethane resins and mixed urethane/urea resins of this inventionare very pure, being free of salts and other insoluble contaminants.This makes the inks made from these materials easy to filter andprovides for high reliability in ink jet printing devices. This is amajor advantage.

(2) The urethane resins and mixed urethane/urea resins of this inventionare specifically tailored to give certain physical properties thatoptimize the performance of the inks of this invention in ink jetprinting devices and on the output substrate. These desirable inkproperties include melting point, viscosity, transparency and thedynamic mechanical properties referenced in the aforementioned U.S. Pat.No. 5,389,958.

(3) The urethane resins and mixed urethane/urea resin of this inventionare used in certain combinations with polyethylene wax and mono-amideingredients to give ink compositions that display an improved yieldstress versus temperature curve over prior art ink compositions. Thisenables ink droplets to be spread and fused at elevated temperaturesduring the fusing and transfer steps in an indirect printing process,but at a lower pressure than was possible with prior art inks, as wellas reducing the coefficient of friction of ink.

(4) The mixtures of urethane resins, mixed urethane/urea resins,monoamide waxes and polyethylene waxes described in this patent provideinks with a low coefficient of friction in the solid phase.

Many other patents describe other materials for use in phase change inkjet inks. Some representative examples include U.S. Pat. Nos. 3,653,932;4,390,369; 4,484,948; 4,684,956; 4,851,045; 5,006,170; 5,151,120; EPApplication Nos. 0187352 and 0206286; and PCT Patent Application WO94/04619. These other materials can include paraffins, microcrystallinewaxes, polyethylene waxes, ester waxes, amide waxes, fatty acids, fattyalcohols, fatty amides and other waxy materials, sulfonamide materials,resinous materials made from different natural sources (tall oil rosinsand rosin esters are an example) and many synthetic resins, oligomers,polymers, co-polymers, and ionomers. It will be obvious to those skilledin the art that the isocyanate-derived materials of this invention couldbe used in inks made from many different combinations of thesematerials.

The aforementioned U.S. Pat. No. 5,496,879 and German patentpublications DE 4205636AL and DE 4205713AL, assigned to SiegwerkFarbenfabrik Keller, Dr. Rung and Co., describe materials used for phasechange or hot melt gravure printing. It will be obvious to those skilledin the art that the isocyanate-derived materials of this currentinvention would be compatible with those materials and could also beused in that application or other similar printing methods that employhot melt ink technology.

It also will be obvious to those skilled in the art that other inkcolors besides the subtractive primary colors are desirable forapplications, such as postal marking or industrial marking and labelingusing phase change printing, and that this invention is applicable tothese needs. Infrared (IR) or ultraviolet (UV) absorbing dyes can alsobe incorporated into the inks of this invention for use in applicationssuch as "invisible" coding or marking of products.

The inks of the present invention can be equally well employed inapparatus for direct or indirect (offset) printing applications. Whenemployed in direct printing applications a suitable method of printingor producing a layer of a phase change colored ink directly on thesurface of a substrate can comprise:

(1) forming a phase change ink composition in the solid phase,comprising an admixture of (a) a phase change carrier compositioncontaining at least one isocyanate-derived resin or wax and (b) a phasechange compatible colorant.

(2) transferring the solid phase, phase change colored ink compositionto a phase change ink application means or print head;

(3) raising the operating temperature of the application means or printhead to a level whereby a liquid phase, phase change colored inkcomposition is formed;

(4) providing a substrate in proximity to the application means;

(5) applying a predetermined pattern of the liquid phase, phase changecolored ink composition to at least one surface of the substrate; and

(6) lowering the temperature of the applied ink composition to form asolid phase, phase change ink pattern on the substrate.

An appropriate direct printing process is described in greater detail inU.S. Pat. No. 5,195,430.

When employed in indirect or offset printing applications a suitablemethod of printing or producing a layer of a phase change colored inkindirectly on the surface of a substrate by transferring from anintermediate transfer surface can comprise:

(1) forming a phase change ink composition in the solid phase,comprising an admixture of (a) a phase change carrier compositioncontaining at least one isocyanate-derived resin or wax and (b) a phasechange compatible colorant.

(2) transferring the solid phase, phase change colored ink compositionto a phase change ink application means or a print head;

(3) raising the operating temperature of the application means or printhead to a level whereby a liquid phase, phase change colored inkcomposition is formed;

(4) providing an intermediate transfer surface in proximity to theapplication means;

(5) applying a predetermined pattern of the liquid phase, phase changecolored ink composition to the intermediate transfer surface;

(6) lowering the temperature of the applied ink composition to form asolid phase, phase change ink pattern on the intermediate transfersurface at a second, intermediate temperature;

(7) transferring said phase change ink composition from the intermediatetransfer surface to a final substrate; and

(8) fixing the phase change ink composition to the substrate to form aprinted substrate, the phase change ink composition having (a) acompressive yield strength which will allow it to be malleable to spreadand deform without an increase in stress when compressive forces areapplied thereto at the second operating temperature, and sufficientinternal cohesive strength to avoid shear banding and weak behavior whensaid phase change ink composition is transferred and fixed to saidsubstrate, and (b) a ductility on the substrate after fixing.

An appropriate offset or indirect printing process is described ingreater detail in U.S. Pat. No. 5,389,958.

The present invention is further described in detail by means of thefollowing Examples and Comparisons. All parts and percentages are byweight and all temperatures are degrees Celsius unless explicitly statedotherwise. It is to be noted that while the following examples mayrecite only one colorant, it is to be understood that each individualexample is only illustrative and any of the primary colorants (cyan,yellow, magenta and black) used in subtractive color printing could beemployed in each instance.

EXAMPLE 1 The Reaction of C-32 Linear Alcohol and IsophoroneDiisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 900.0 grams (1.714 moles) of a C-32 linearalcohol¹ and about 169.1 grams (0.762 moles) of isophorone diisocyanate²to the addition funnel. The alcohol was heated to 130° C. and agitationbegun. The isophorone diisocyanate was added in approximately 13minutes. About 0.22 grams of dibutyltindilaurate³ was added and thereaction mixture heated to about 145° C. After 2 hours at 145° an FT-IRof the reaction product was run to insure all of the NCO functionalitywas consumed. The absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ correspondingto urethane frequencies was used to confirm this. The final urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 12.5 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. A T_(g) for this material was not observedas measured by Differential Scanning Calorimetry using a DuPont 2100calorimeter at a scan rate of 20° C./minute.

EXAMPLE 2 The Reaction Product of C-40 Linear Alcohol and YellowReactive Colorant with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, and thermocouple-temperature controller was added about 20.5grams (0.056 equiv.) of a yellow polymeric colorant¹ and about 25.0grams (0.225 equiv.) of isophorone diisocyanate². This mixture wasagitated without heating under nitrogen. After 1 hour the temperaturewas raised to about 50° C. and stirring continued. After 45 minutes,about 0.22 grams of dibutyltindilaurate⁶ was added and the reactionmixture was heated to about 60° C. After 1 hour at 60° C. , about 114grams (0.169 equiv.) of a C-40 linear alcohol⁴ was added and thereaction mixture was heated to about 135° C. After about 1 hour an FT-IRof the reaction product was run to insure all of the NCO functionalitywas consumed. The absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ correspondingto urethane frequencies was used to confirm this. The final mixedurethane resin product was then poured into aluminum molds and allowedto cool and harden. This final product was a yellow solid resin at roomtemperature characterized by the following physical properties:viscosity of about 45 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. The T_(g) and spectral strength of thismaterial were not measured.

EXAMPLE 3 The Reaction Product of C-50 Linear Alcohol and YellowReactive Colorant with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, and thermocouple-temperature controller was added about 24.6grams (0.067 equiv.) of a yellow polymeric colorant¹ and about 25.0grams (0.225 equiv.) of isophorone diisocyanate². This mixture wasagitated without heating under nitrogen. After 30 minutes, about 0.22grams of dibutyltindilaurate⁶ was added and the mixture was agitatedwithout heating under nitrogen. After 30 minutes the temperature wasraised to about 50° C. and stirring continued. After 30 minutes thereaction mixture was heated to about 100° C. After 30 minutes, about136.1 grams (0.158 equiv.) of a C-50 linear alcohol¹ was added and thereaction mixture was heated to about 135° C. After about 1 hour a FT-IRof the reaction product was run to insure all of the NCO functionalitywas consumed. The absence (disappearance) of a peak at about 2285 cm⁻¹(NCO) and the appearance (or increase in magnitude) of peaks at about1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ correspondingto urethane frequencies was used to confirm this. The final mixedurethane resin product was then poured into aluminum molds and allowedto cool and harden. This final product was a yellow solid resin at roomtemperature characterized by the following physical properties:viscosity of about 158 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. The Tg and spectral strength of thismaterial were not measured.

EXAMPLE 4 The Reaction Product of C-40 Linear Alcohol and IsophoroneDiisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 610 grams (0.904 moles) of a C-40 linearalcohol¹ and about 100.0 grams (0.450 moles) of isophorone diisocyanate²to the addition funnel. The alcohol mixture was heated to 100° C. andagitation begun. The isophorone diisocyanate was added in approximately5 minutes. About 0.22 grams of dibutyltindilaurate³ was added and thereaction mixture heated to about 135° C. After 2 hours, an FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final urethane resinproduct was then poured into aluminum molds and allowed to cool andharden. This final product was a clear solid resin/wax at roomtemperature characterized by the following physical properties:viscosity of about 21 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. A T_(g) for this material was not observedas measured by Differential Scanning Calorimetry using a DuPont 2100calorimeter at a scan rate of 20° C./minute.

EXAMPLE 5 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate and C-30 Linear Alcohol with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 250.0 grams of stearyl stearamide¹, about144.0 grams (0.560 moles) of octylphenol ethoxylate², about 84.0 grams(0.234 moles) of hydroabietyl alcohol³, about 91.0 grams (0.173 moles)of C-32 linear alcohol⁴ and about 111.5 grams (0.502 moles) ofisophorone diisocyanate⁵ to the addition funnel. This mixture was heatedto 125° C. and agitation begun when all components were molten (atapprox. 100° C.). The isophorone diisocyanate was added in approximately2 minutes. About 0.22 grams of dibutyltindilaurate⁶ was added and thereaction mixture heated to about 150° C. After 2 hours at 150° C., about15.0 grams (0.058 moles) of octylphenol ethoxylate², about 15.5 grams(0.044 moles) of hydroabietyl alcohol³, about 15.0 grams (0.029 moles)of C-32 linear alcohol⁴ and about 0.05 grams of dibutyltindilaurate⁶were added and the reaction mixture heated at about 150° C. for 1 hour.A FT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹corresponding to urethane frequencies was used to confirm this. Thefinal mixed urethane resin/wax product was then poured into aluminummolds and allowed to cool and harden. This final product was a clearsolid resin/wax at room temperature characterized by the followingphysical properties: viscosity of about 13.01 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C. The T_(g) ofthis material was not measured.

EXAMPLE 6 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, and Yellow Reactive Colorant withIsophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 250.0 grams of stearyl stearamide¹, about131.0 grams (0.509 equiv.) of octylphenol ethoxylate², about 65.0 grams(0.184 equiv.) of hydroabietyl alcohol³, about 71.3 grams (0.136 equiv.)of C-32 linear alcohol⁴ and about 106.0 grams (0.955 equiv.) ofisophorone diisocyanate⁵ to the addition funnel. This mixture was heatedto 145° C. and agitation begun when all components were molten (atapprox. 100° C.). The isophorone diisocyanate was added in approximately2 minutes. About 0.22 grams of dibutyltindilaurate⁶ was added and thereaction mixture was maintained at about 145° C. After 1 hour at 145°C., about 40.8 grams (0.0591 equiv.) of a yellow polymeric colorantcorresponding to Colorant A from Table I of U.S. Pat. No. 5,231,135 andabout 0.05 grams of dibutyltindilaurate⁶ were added and the reactionmixture was maintained at about 145° C. After 1 hour, about 15.0 grams(0.058 equiv.) of octylphenol ethoxylate², about 15.0 grams (0.042equiv.) of hydroabietyl alcohol³, about 15.0 grams (0.029 equiv.) ofC-32 linear alcohol⁴ and about 0.05 grams of dibutyltindilaurate⁶ wereadded and the reaction mixture was maintained at about 150° C. for 1hour. A FT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹corresponding to urethane frequencies was used to confirm this. Thefinal mixed urethane resin product was then poured into aluminum moldsand allowed to cool and harden. This final product was a yellow solidresin at room temperature characterized by the following physicalproperties: viscosity of about 15 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 140° C. The T_(g) and spectral strengthof this material were not measured.

EXAMPLE 7 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, and Cyan Reactive Colorant withIsophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 200.0 grams of stearyl stearamide¹, about104.8 grams (0.408 equiv.) of octylphenol ethoxylate², about 54.6 grams(0.154 equiv.) of hydroabietyl alcohol³, about 57.6 grams (0.110 equiv.)of C-32 linear alcohol⁴ and about 87.4 grams (0.787 equiv.) ofisophorone diisocyanate⁵ to the addition funnel. This mixture was heatedto 125° C. and agitation begun when all components were molten (atapprox. 100° C.) under nitrogen. The isophorone diisocyanate was addedin approximately 2 minutes. About 0.22 grams of dibutyltindilaurate⁶ wasadded and the reaction mixture heated at about 145° C. After 1 hourabout 11.5 grams (0.0226 equiv.) of a cyan polymeric colorant⁷ and about0.05 grams of dibutyltindilaurate⁶ were addehand the reaction mixtureheated at about 145° C. After 1 hour about 15.0 grams (0.058 equiv.) ofoctylphenol ethoxylate², about 15.5 grams (0.044 equiv.) of hydroabietylalcohol³, about 15.0 grams (0.029 equiv.) of C-32 linear alcohol⁴ andabout 0.05 grams of dibutyltindilaurate⁶ were added and the reactionmixture heated at about 145° C. for 1 hour. A FT-IR of the reactionproduct was run to insure all of the NCO functionality was consumed. Theabsence (disappearance) of a peak at about 2285 cm⁻¹ (NCO) and theappearance (or increase in magnitude) of peaks at about 1740 to about1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding to urethanefrequencies were used to confirm this. The final mixed urethane resinproduct was then poured into aluminum molds and allowed to cool andharden. This final product was a cyan solid resin at room temperaturecharacterized by the following physical properties: viscosity of about15.6 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C. The T_(g) and spectral of this material were not measured.

EXAMPLE 8 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, Yellow Reactive Colorant, andPolycarbonate Polyol with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 34.7 grams (0.186 equiv.) of octylphenolethoxylate¹, about 47.8 grams (0.135 equiv.) of hydroabietyl alcohol²,about 57.0 grams (0.109 equiv.) of C-32 linear alcohol³ and about 50.0grams (0.450 equiv.) of isophorone diisocyanate⁴ to the addition funnel.This mixture was heated to 125° C. and agitation begun when allcomponents were molten (at approx. 100° C.). The isophorone diisocyanatewas added in approximately 2 minutes. About 0.15 grams ofdibutyltindilaurate⁵ was added and the reaction mixture heated to about160° C. After 1 hour at 160° C., about 22.4 grams (0.023 equiv.) ofpolycarbonate polyol⁶ and about 0.05 grams of dibutyltindilaurate⁶ wereadded and the reaction mixture was heated to about 170° C. After 1 hourat 170° C., about 15.7 grams (0.023 equiv.) of a yellow polymericcolorant corresponding to Colorant A from Table I of U.S. Pat. No.5,231,135 and about 0.05 grams of dibutyltindilaurate⁶ were added andthe reaction mixture was heated at about 170° C. After 1 hour at 170°C., about 17.0 grams (0.032 equiv.) C-32 linear alcohol³ was added andthe reaction mixture was heated at about 170° C. After 1 hour at 170° C.a FT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹corresponding to urethane frequencies was used to confirm this. Thefinal mixed urethane resin product was then poured into aluminum moldsand allowed to cool and harden. This final product was a yellow solidresin at room temperature characterized by the following physicalproperties: viscosity of about 429 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 140° C. The T_(g) and spectral strengthof this material were not measured.

EXAMPLE 9 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, Cyan Reactive Colorant, andPolycarbonate Polyol with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 34.7 grams (0.186 equiv.) of octylphenolethoxylate¹, about 47.8 grams (0.135 equiv.) of hydroabietyl alcohol²,about 57.0 grams (0.109 equiv.) of C-32 linear alcohol³ and about 50.0grams (0.450 equiv.) of isophorone diisocyanate⁴ to the addition funnel.This mixture was heated to 125° C. and agitation begun when allcomponents were molten (at approx. 100° C.). The isophorone diisocyanatewas added in approximately 2 minutes. About 0.15 grams ofdibutyltindilaurate⁵ was added and the reaction mixture heated to about160° C. After 1 hour at 160° C., about 22.4 grams (0.023 equiv.) ofpolycarbonate polyol⁶ and about 0.05 grams of dibutyltindilaurate⁶ wereadded and the reaction mixture was heated to about 170° C. After 1 hourat 170° C., about 11.5 grams (0.23 equiv.) of a cyan polymeric colorant⁷and about 0.05 grams of dibutyltindilaurate⁶ were added and the reactionmixture was heated at about 170° C. After 1 hour at 170° C., about 17.0grams (0.032 equiv.) C-32 linear alcohol³ was added and the reactionmixture was heated at about 170° C. After 1 hour at 170° C. a FT-IR ofthe reaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a cyan solid resin at roomtemperature characterized by the following physical properties:viscosity of about 11.9 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. The T_(g) and spectral strength of thismaterial were not measured.

EXAMPLE 10 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, and 0.1 Equivalents PolycarbonatePolyol with Isophorone Diisocyanate

To a 3000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel, and thermocouple-temperature controller wasadded about 294.0 grams (1.140 moles) of octylphenol ethoxylate¹, about400.0 grams (1.140 moles) of hydroabietyl alcohol², about 479.0 grams(0.912 moles) of C-32 linear alcohol³ and about 400.0 grams (1.80 moles)of isophorone diisocyanate⁴ to the addition funnel. This mixture washeated to 125° C. and agitation begun when all components were molten(at approx. 100° C.). The isophorone diisocyanate was added inapproximately 10 minutes. About 1.2 grams of dibutyltindilaurate⁵ wasadded and the reaction mixture heated to about 150° C. After 1 hour,about 179.0 grams (0.090 moles) of polycarbonate polyol⁶ and about 0.10grams of dibutyltindilaurate⁶ were added and the reaction mixture washeated to about 170° C. After 1 hour at 170° C., about 133.0 grams(0.253 moles) of a C-32 linear alcohol³ was added and the reactionmixture was heated at about 170° C. After 1 hour at 170° C. a FT-IR ofthe reaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a colorless solid resin at roomtemperature characterized by the following physical properties:viscosity of about 38.4 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a Tg of about 18° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).

EXAMPLE 11 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, and 0.2 Equivalents PolycarbonatePolyol with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel, and thermocouple-temperature controller wasadded about 69.5 grams (0.270 moles) of octylphenol ethoxylate¹, about95.7 grams (0.270 moles) of hydroabietyl alcohol², about 130.0 grams(0.248 moles) of C-32 linear alcohol³ and about 100.0 grams (0.450moles) of isophorone diisocyanate⁴ to the addition funnel. This mixturewas heated to 125° C. and agitation begun when all components weremolten (at approx. 100° C.). The isophorone diisocyanate was added inapproximately 3 minutes. About 0.22 grams of dibutyltindilaurate⁵ wasadded and the reaction mixture heated to about 150° C. After 1 hour,about 89.6 grams (0.045 moles) of polycarbonate polyol⁶ and about 0.10grams of dibutyltindilaurate⁶ were added and the reaction mixture washeated to about 160° C. After 1 hour, about 15.0 grams (0.029 moles) ofa C-32 linear alcohol³ was added and the reaction mixture was heated atabout 160° C. After 1 hour, a FT-IR of the reaction product was run toinsure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740 to about 1680 cm⁻¹ andabout 1540 to about 1530 cm⁻¹ corresponding to urethane frequencies wasused to confirm this. The final mixed urethane resin product was thenpoured into aluminum molds and allowed to cool and harden. This finalproduct was a colorless solid resin at room temperature characterized bythe following physical properties: viscosity of about 50 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., and a Tgof about 14° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII).

EXAMPLE 12 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, and 0.3 Equivalents PolycarbonatePolyol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.6 grams (0.0257 moles) of octylphenol ethoxylate¹, about 9.0 grams(0.0254 equiv.) of hydroabietyl alcohol², and about 12.0 grams (0.0229moles) of C-32 linear alcohol³. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁴ and about0.05 grams of dibutyltindilaurate⁵ were added and the reaction mixtureheated to about 150° C. After 2 hours about 13.4 grams (0.007 moles) ofpolycarbonate polyol⁶ and about 0.05 grams of dibutyltindilaurate⁵ wereadded and the reaction mixture heated to about 170° C. After about 2hours about 1.4 grams (0.0027 moles) of C-32 linear alcohol³ a FT-IR ofthe reaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 56.6 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 10.9° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII).

EXAMPLE 13 The Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, and 0.4 Equivalents PolycarbonatePolyol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.2 grams (0.0241 moles) of octylphenol ethoxylate¹, about 8.5 grams(0.0240 equiv.) of hydroabietyl alcohol², and about 11.4 grams (0.0217moles) of C-32 linear alcohol³. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁴ and about0.05 grams of dibutyltindilaurate⁵ were added and the reaction mixtureheated to about 150° C. After 2 hours about 17.9 grams (0.009 moles) ofpolycarbonate polyol⁶ and about 0.05 grams of dibutyltindilaurate⁵ wereadded and the reaction mixture heated to about 170° C. After about 2hours about 1.3 grams (0.0025 moles) of C-32 linear alcohol³ a FT-IR ofthe reaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 96.4 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 3.1° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).

EXAMPLE 14 Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, Yellow Reactant Colorant, C-50 LinearAlcohol Ethoxylate and Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 32.8 grams (0.128 equiv.) of octylphenolethoxylate¹, about 46.2 grams (0.128 equiv.) of hydroabietyl alcohol²,about 67.0 grams (0.128 equiv.) of C-32 linear alcohol³, about 76.6grams (0.045 equiv.) of C-50 linear alcohol ethoxylate⁴, about 15.7grams (0.023 equiv.) of a yellow polymeric colorant corresponding toColorant A from Table I of U.S. Pat. No. 5,231,135, and about 50.0 grams(0.450 equiv.) of isophorone diisocyanate⁵ to the addition funnel. Thismixture was heated to 120° C. and agitation begun when all componentswere molten (at approx. 100° C.). The isophorone diisocyanate was addedin approximately 2 minutes. About 0.22 grams of dibutyltindilaurate⁶ wasadded and the reaction mixture heated to about 150° C. After 2 hours at150° C., about 4.0 grams (0.008 equiv.) of C-32 linear alcohol³ wasadded and the reaction mixture heated at about 150° C. for 1 hour. AFT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) and the appearance (or increase in magnitude) ofpeaks at about 1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹corresponding to urethane frequencies was used to confirm this. Thefinal mixed urethane resin product was then poured into aluminum moldsand allowed to cool and harden. This final product was a yellow solidresin at room temperature characterized by the following physicalproperties: viscosity of about 340 cPs as measured by a Ferranti-Shirleycone-plate viscometer at about 140° C. The T_(g) and spectral strengthof this material were not measured.

EXAMPLE 15 The Reactant Product of Hydroabietic Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, C-50 Linear Alcohol Ethoxylate, CyanReactive Colorant, and Isophorone Diisocyanate

To a 1000 ml four-neck kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 32.8 grams (0.128 equiv.) of octylphenolethoxylate¹, about 46.2 grams (0.128 equiv.) of hydroabietyl alcohol²,about 67.0 grams (0.128 equiv.) of C-32 linear alcohol³, about 76.6grams (0.045 equiv.) of C-50 linear alcohol ethoxylate⁴, and about 50.0grams (0.450 equiv.) of isophorone diisocyanate⁵ to the addition funnel.This mixture was heated to 120° C. and agitation begun when allcomponents were molten (at approx. 100° C.). The isophorone diisocyanatewas added in approximately 2 minutes. About 0.22 grams ofdibutyltindilaurate⁶ was added and the reaction mixture heated to about150° C. After 2 hours at 150° C., about 11.5 grams (0.023 equiv.) of acyan polymeric colorant⁷ was added and the reaction mixture heated atabout 150° C. After 1 hours at 150° C., about 4.0 grams (0.008 equiv.)of C-32 linear alcohol³ was added and the reaction mixture heated atabout 150° C. for 1 hour. A FT-IR of the reaction product was run toinsure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740 to about 1680 cm⁻¹ andabout 1540 to about 1530 cm¹ corresponding to urethane frequencies wasused to confirm this. The final mixed urethane resin product was thenpoured into aluminum molds and allowed to cool and harden. This finalproduct was a cyan solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 38 cPs as measured bya Ferranti-Shirley cone-plate viscometer at about 140° C. The T_(g) andspectral strength of this material were not measured.

EXAMPLE 16 The Reactant Product of Hydroabietic Alcohol, OctylphenolEthoxylate, C-32 Linear Alcohol, C-50 Linear Alcohol Ethoxylate, CyanReactive Colorant, and Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 31.0 grams (0.120 equiv.) of octylphenolethoxylate¹, about 43.5 grams (0.120 equiv.) of hydroabietyl alcohol²,about 52.0 grams (0.099 equiv.) of C-32 linear alcohol³, about 114.9grams (0.068 equiv.) of C-50 linear alcohol ethoxylate⁴, and about 50.0grams (0.450 equiv.) of isophorone diisocyanate⁵ to the addition funnel.This mixture was heated to 120° C. and agitation begun when allcomponents were molten (at approx. 100° C.). The isophorone diisocyanatewas added in approximately 2 minutes. About 0.22 grams ofdibutyltindilaurate⁶ was added and the reaction mixture heated to about150° C. After 2 hours at 150° C., about 11.5 grams (0.023 equiv.) of ahydroxyl containing cyan polymeric reactive colorant⁷ was added and thereaction mixture heated at about 150° C. After 1 hours at 150° C., about13.0 grams (0.025 equiv.) of C-32 linear alcohol³ was added and thereaction mixture heated at about 150° C. for 1 hour. A FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a cyan solid resin at roomtemperature characterized by the following physical properties:viscosity of about 12.5 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. The T_(g) and spectral strength of thismaterial were not measured.

EXAMPLE 17 Reaction Product of Hydroabietic Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.2 Equivalents of C-50 LinearAlcohol Ethoxylate with Isophorone Diisocyanate

To a 3000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel and thermocouple-temperature controller wasadded about 243.0 grams (0.946 moles) of octylphenol ethoxylate¹, about343.0 grams (0.947 moles) of hydroabietyl alcohol², about 497.0 grams(0.947 moles) of C-32 linear alcohol³, about 536 grams (0.315 moles) ofC-50 linear alcohol ethoxylate⁴, and about 350.0 grams (1.577 moles) ofisophorone diisocyanate⁵ to the addition funnel. This mixture was heatedto 120° C. and agitation begun when all components were molten (atapprox. 100° C.). The isophorone diisocyanate was added in approximately10 minutes. About 0.80 grams of dibutyltindilaurate⁶ was added and thereaction mixture heated to about 150° C. After 2 hours at an FT-IR ofthe reaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 31 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C. and a Tg of about 3° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).

EXAMPLE 18 Reaction Product of Hydroabietic Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.1 Equivalents of C-50 LinearAlcohol Ethoxylate with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.3 grams (0.0284 moles) of octylphenol ethoxylate¹, about 10.1 grams(0.0285 equiv.) of hydroabietyl alcohol², about 15.0 grams (0.0286moles) of C-32 linear alcohol³, and about 7.7 grams (0.0045 moles) ofC-50 linear alcohol ethoxylate⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 30.5 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 2.8° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids analyzer (RSAII).

EXAMPLE 19 Reaction Product of Hydroabietic Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.3 Equivalents of C-50 LinearAlcohol Ethoxylate with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.6 grams (0.0257 moles) of octylphenol ethoxylate¹, about 9.2 grams(0.0254 equiv.) of hydroabietyl alcohol², about 13.4 grams (0.0255moles) of C-32 linear alcohol³, and about 23.0 grams (0.0135 moles) ofC-50 linear alcohol ethoxylate⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about1740-1680 cm⁻¹ and about 1540-1530 cm⁻¹ corresponding to urethanefrequencies was used to confirm this. The final mixed urethane resinproduct was then poured into aluminum molds and allowed to cool andharden. This final product was a clear solid resin at room temperaturecharacterized by the following physical properties: viscosity of about29.8 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C., and a T_(g) of about 12.9° C. as measured by DynamicMechanical Analysis using a Rheometrics Solids Analyzer (RSAII).

EXAMPLE 20 Reaction Product of Hydroabietic Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.4 Equivalents of C-50 LinearAlcohol Ethoxylate with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.2 grams (0.0241 moles) of octylphenol ethoxylate¹, about 8.7 grams(0.0240 equiv.) of hydroabietyl alcohol², about 12.6 grams (0.0240moles) of C-32 linear alcohol³, and about 30.6 grams (0.0180 moles) ofC-50 linear alcohol ethoxylate⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 32.7 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about -21.9° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII).

EXAMPLE 21 Reaction Product of Hydroabietyl Alcohols, OctyiphenolEthoxylate, C-30 Linear Alcohol, 2-Hexadecyleicosanol, and YellowReactive Colorant with Isophorone Diisocyanate

To a 1000 ml four-neck resin kettle equipped with a Trubore stirrer, N₂atmosphere, addition funnel (200 ml), and thermocouple-temperaturecontroller was added about 31.0 grams (0.120 equiv.) of octylphenolethoxylate¹, about 43.5 grams (0.120 equiv.) of hydroabietyl alcohol²,about 63.0 grams (0.120 equiv.) of C-32 linear alcohol³, about 23.0grams (0.045 equiv.) of 2-hexadecyleicosanol, about 5.7 grams (0.0225equiv.) of a yellow polymeric colorant corresponding to Colorant A fromTable I of U.S. Pat. No. 5,231,135, and about 50.0 grams (0.450 equiv.)of isophorone diisocyanate⁵ to the addition funnel. This mixture washeated to 120° C. and agitation begun when all components were molten(at approx. 100° C.). The isophorone diisocyanate was added inapproximately 2 minutes. About 0.22 grams of dibutyltindilaurate⁶ wasadded and the reaction mixture heated to about 150° C. After 2 hours at150° C., about 4.0 grams (0.008 equiv.) of C-32 linear alcohol³ wasadded and the reaction mixture heated at about 150° C. for 1 hour. AFT-IR of the reaction product was run to insure all of the NCOfunctionality was consumed. The absence (disappearance) of a peak atabout 2285 cm⁻¹ (NCO) a nd the appearance (or increase in magnitude) ofpeaks at about 1740 to about 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹corresponding to urethane frequencies was used to confirm this. Thefinal mixed urethane resin product was then poured into aluminum moldsand allowed to cool and harden. This final product was a yellow solidresin at room temperature characterized by the following physicalproperties: viscosity of about 32.1 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C. The T_(g) andspectral strength of this material were not measured.

EXAMPLE 22 Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.1 Equivalents of2-Hexadecyleicosanol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.3 grams (0.0284 moles) of octylphenol ethoxylate¹, about 10.1 grams(0.0285 equiv.) of hydroabietyl alcohol², about 15.0 grams (0.0286moles) of C-32 linear alcohol³, and about 2.3 grams (0.0045 moles) of2-hexadecyleicosanol⁴. This mixture was heated to 120° C. and agitationbegun when all components were molten (at approx. 100° C.). About 10.0grams (0.045 moles) of isophorone diisocyanate⁵ and about 0.05 grams ofdibutyltindilaurate⁶ were added and the reaction mixture heated to about150° C. After 2 hours at 150° C., a FT-IR of the reaction product wasrun to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740 to about 1680 cm⁻¹ andabout 1540 to about 1530 cm⁻¹ corresponding to urethane frequencies wasused to confirm this. The final mixed urethane resin product was thenpoured into aluminum molds and allowed to cool and harden. This finalproduct was a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 30 cPs as measured bya Ferranti-Shirley cone-plate viscometer at about 140° C., a T_(g) ofabout 17.3° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII).

EXAMPLE 23 Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.2 Equivalents of2-Hexadecyleicosanol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.0 grams (0.0272 moles) of octylphenol ethoxylate¹, about 9.6 grams(0.0271 equiv.) of hydroabietyl alcohol², about 14.2 grams (0.0270moles) of C-32 linear alcohol³, and about 4.6 grams (0.0090 moles) of2-hexadecyleicosanol⁴. This mixture was heated to 120° C. and agitationbegun when all components were molten (at approx. 100° C.). About 10.0grams (0.045 moles) of isophorone diisocyanate⁵ and about 0.05 grams ofdibutyltindilaurate⁶ were added and the reaction mixture heated to about150° C. After 2 hours at 150° C., a FT-IR of the reaction product wasrun to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740 to about 1680 cm⁻¹ andabout 1540 to about 1530 cm⁻¹ corresponding to urethane frequencies wasused to confirm this. The final mixed urethane resin product was thenpoured into aluminum molds and allowed to cool and harden. This finalproduct was a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 27.7 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a T_(g) ofabout 7.9° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII).

EXAMPLE 24 Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.3 Equivalents of2-Hexadecyleicosanol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.6 grams (0.0257 moles) of octylphenol ethoxylate¹, about 9.0 grams(0.0254 equiv.) of hydroabietyl alcohol², about 13.4 grams (0.0255moles) of C-32 linear alcohol³, and about 6.9 grams (0.0135 moles) of2-hexadecyleicosanol⁴. This mixture was heated to 120° C. and agitationbegun when all components were molten (at approx. 100° C.). About 10.0grams (0.045 moles) of isophorone diisocyanate⁵ and about 0.05 grams ofdibutyltindilaurate⁶ were added and the reaction mixture heated to about150° C. After 2 hours at 150° C., a FT-IR of the reaction product wasrun to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740 to about 1680 cm⁻¹ andabout 1540 to about 1530 cm⁻¹ corresponding to urethane frequencies wasused to confirm this. The final mixed urethane resin product was thenpoured into aluminum molds and allowed to cool and harden. This finalproduct was a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 26.4 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a T_(g) ofabout 7.1° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII).

EXAMPLE 25 Reaction Product of Hydroabietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.4 Equivalents of2-Hexadecyleicosanol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.2 grams (0.0241 moles) of octylphenol ethoxylate¹, about 8.5 grams(0.0240 equiv.) of hydroabietyl alcohol², about 12.6 grams (0.0240moles) of C-32 linear alcohol³, and about 9.2 grams (0.0180 moles) of2-hexadecyleicosanol⁴. This mixture was heated to 120° C. and agitationbegun when all components were molten (at approx. 100° C.). About 10.0grams (0.045 moles) of isophorone diisocyanate⁵ and about 0.05 grams ofdibutyltindilaurate⁶ were added and the reaction mixture heated to about150° C. After 2 hours at 150° C., a FT-IR of the reaction product wasrun to insure all of the NCO functionality was consumed. The absence(disappearance) of a peak at about 2285 cm⁻¹ (NCO) and the appearance(or increase in magnitude) of peaks at about 1740 to about 1680 cm⁻¹ andabout 1540 to about 1530 cm⁻¹ corresponding to urethane frequencies wasused to confirm this. The final mixed urethane resin product was thenpoured into aluminum molds and allowed to cool and harden. This finalproduct was a clear solid resin at room temperature characterized by thefollowing physical properties: viscosity of about 25.0 cPs as measuredby a Ferranti-Shirley cone-plate viscometer at about 140° C., a T_(g) ofabout 6° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII).

EXAMPLE 26 The Reaction Product of Abietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.1 Equivalents ofPoly(ethylene/butylene) mono-alcohol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.3 grams (0.0284 moles) of octylphenol ethoxylate¹, about 10.3 grams(0.0285 equiv.) of hydroabietyl alcohol², about 15.0 grams (0.0286moles) of C-32 linear alcohol³, and about 21.0 grams (0.0045 moles) ofpoly(ethylene/butylene) mono-ol⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 72 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about -47.6° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII).

EXAMPLE 27 The Reaction Product of Abietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.2 Equivalents ofPoly(ethylene/butylene) mono-alcohol with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.0 grams (0.0272 moles) of octylphenol ethoxylate¹, about 9.8 grams(0.0271 equiv.) of hydroabietyl alcohol², about 14.2 grams (0.0270moles) of C-32 linear alcohol³, and about 42.0 grams (0.0090 moles) ofpoly(ethylene/butylene) mono-ol⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 17401680cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding to urethanefrequencies was used to confirm this. The final mixed urethane resinproduct was then poured into aluminum molds and allowed to cool andharden. This final product was a clear solid resin at room temperaturecharacterized by the following physical properties: viscosity of about105 cPs as measured by a Ferranti-Shirley cone-plate viscometer at about140° C. The T_(g) of this example could not be measured because it wasso soft as to the intractable.

EXAMPLE 28 The Reaction Product of Abietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.1 Equivalents of Polyoxyethylene(2) Stearyl Ether with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.3 grams (0.0284 moles) of octylphenol ethoxylate¹, about 10.3 grams(0.0285 equiv.) of hydroabietyl alcohol², about 15.0 grams (0.0286moles) of C-32 linear alcohol³, and about 1.6 grams (0.0045 moles) ofpolyoxyethylene(2) stearylether⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 31.0 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 19.9° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII).

EXAMPLE 29 The Reaction Product of Abietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.2 Equivalents of Polyoxyethylene(2) Stearyl Ether with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about7.0 grams (0.0272 moles) of octylphenol ethoxylate¹, about 9.8 grams(0.0271 equiv.) of hydroabietyl alcohol², about 14.2 grams (0.0270moles) of C-32 linear alcohol³, and about 3.2 grams (0.0090 moles)polyoxyethylene(2) stearyl ether⁴. This mixture was heated to 120° C.and agitation begun when all components were molten (at approx. 100°C.). About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ andabout 0.05 grams of dibutyltindilaurate⁶ were added and the reactionmixture heated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 28.4 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 12.5° C. as measuredby Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer(RSAII).

EXAMPLE 30 The Reaction Product of Abietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.3 Equivalents of Polyoxyethylene(2) Stearyl Ether with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.6 grams (0.0257 moles) of octylphenol ethoxylate¹, about 9.2 grams(0.0254 equiv.) of hydroabietyl alcohol², about 13.4 grams (0.0255moles) of C-32 linear alcohol³, and about 4.8 grams (0.0135 moles) ofpolyoxyethylene(2)stearyl ether⁴. This mixture was heated to 120° C. andagitation begun when all components were molten (at approx. 100° C.).About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ and about0.05 grams of dibutyltindilaurate⁶ were added and the reaction mixtureheated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 26.0 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 4.2° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).

EXAMPLE 31 The Reaction Product of Abietyl Alcohol, OctylphenolEthoxylate, C-30 Linear Alcohol, and 0.4 Equivalents of Polyoxyethylene(2) Stearyl Ether with Isophorone Diisocyanate

To a 140 ml beaker equipped with teflon coated magnetic stir bar andplaced in a silicone oil bath on a stirring hot plate was added about6.2 grams (0.0241 moles) of octylphenol ethoxylate¹, about 8.7 grams(0.0240 equiv.) of hydroabietyl alcohol², about 12.6 grams (0.0240moles) of C-32 linear alcohol³, and about 6.5 grams (0.0180 moles) ofpolyoxyethylene(2) stearyl ether⁴. This mixture was heated to 120° C.and agitation begun when all components were molten (at approx. 100°C.). About 10.0 grams (0.045 moles) of isophorone diisocyanate⁵ andabout 0.05 grams of dibutyltindilaurate⁶ were added and the reactionmixture heated to about 150° C. After 2 hours at 150° C., a FT-IR of thereaction product was run to insure all of the NCO functionality wasconsumed. The absence (disappearance) of a peak at about 2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at about 1740 toabout 1680 cm⁻¹ and about 1540 to about 1530 cm⁻¹ corresponding tourethane frequencies was used to confirm this. The final mixed urethaneresin product was then poured into aluminum molds and allowed to cooland harden. This final product was a clear solid resin at roomtemperature characterized by the following physical properties:viscosity of about 24.9 cPs as measured by a Ferranti-Shirley cone-plateviscometer at about 140° C., and a T_(g) of about 7.6° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).

EXAMPLE 32 Yellow Polyethylene Wax-Based Ink

In a stainless steel beaker were combined 100 grams of the material fromExample 1, 100 grams of the material from Example 2 and 292 grams ofPolywax PE850¹. The materials were melted overnight at 125° C., thenblended by stirring in a temperature controlled mantle for 1hr at 125°C. The ink was then filtered through a heated (125° C.) Mott apparatus(available from Mott Mettalurgical) using a 2μ filter at 5 psi. Thefiltered polyethylene-based ink was poured into molds and allowed tosolidify to form ink sticks. This final yellow ink product wascharacterized by the following physical properties: viscosity of about13.5 cPs at 140° C. as measured by a Ferranti-Shirley cone-plateviscometer, a melting point of about 150° C. as measured by differentialscanning calorimetry using a DuPont 2100 calorimeter and a T_(g) ofabout 20° C. as measured by Dynamic Mechanical Analysis using aRheometrics Solids Analyzer (RSAII). The spectral strength of this inkwas not measured. This ink was placed in a lab prototype Phaser® 340printer which uses an offset transfer printing process. The ink wasprinted using a print head temperature of 155° C., a drum temperature of85° C. and a paper preheat temperature of 114° C. The finished printswere found to have a coefficient of friction against glass of about 0.6as measured by a Thwing-Albert Friction/Peel Tester (Model 225-1). Thefinished prints were also found to feed reliably in several differentoffice photocopy machines including models. However, the durability ofthe finished prints was poor as evidenced by excessive flaking of inkwhen the prints were folded and a poor resistance to damage fromscratching.

EXAMPLE 33 Yellow Hybrid Ink Formed From Physical Mixture ofPolyethylene Based Ink and Amide Wax Based Ink

In a stainless steel beaker were combined 74 grams of the ink fromExample 12 of U.S. patent application Ser. No. 08/672,617; now U.S. Pat.No. 5,780,528 (issued Jul. 14, 1998), and 90 grams of the ink fromExample 32 above. The inks were melted for 3 hours at 125° C., thenblended by stirring in a temperature controlled mantle for 1/2 hr at125° C. The ink was then filtered through a heated (125° C.) Mottapparatus (available from Mott Mettalurgical) using a 2μ filter at 5psi. The filtered ink mixture was poured into molds and allowed tosolidify to form ink sticks. This final yellow ink product wascharacterized by the following physical properties: viscosity of about13.2 cPs at 140° C. as measured by a Ferranti-Shirley cone-plateviscometer, two melting points at about 91° C. and about 105° C. asmeasured by differential scanning calorimetry using a DuPont 2100calorimeter and a Tg of about 25° C. as measured by Dynamic MechanicalAnalysis using a Rheometrics Solids Analyzer (RSAII). The spectralstrength of this ink was not measured. This ink was placed in a Phaser®340 printer which uses an offset transfer printing process. The ink wasprinted using a print head temperature of 140° C., a drum temperature of60° C. and a paper preheat temperature of 60° C. The finished printswere found to have a coefficient of friction against glass that variedfrom about 0.6-1.4 as measured by a Thwing-Albert Friction/Peel Tester(Model 225-1). This is compared to a COF of about 2.6 for the amide waxbased ink of the above patent Example 12 of the aforementionedapplication when that composition was printed separately under the sameconditions. The finished prints were also found to have much betterresistance to flaking of the ink when folded than the ink from Example33 and good scratch resistance. Testing of the finished prints inphotocopiers gave variable results, but the prints would feed in somemachines. This was a marked improvement over the performance of theprints made from the amide wax based ink composition by itself Thoseprints would not feed in any of the photocopiers tested.

EXAMPLE 34 Cyan Hybrid Ink Made From a Mixture of Urethane Resins and aMixture of Waxes

In a stainless steel beaker were combined 248 grams of the cyan coloredurethane resin from Example 2 of co-pending U.S. patent application Ser.No. 08/672,617 now U.S. Pat. No. 5,780,528 (issued Jul. 14, 1998),; 124grams of the urethane resin from Example 1, 124 grams of theurethane/urea resin from Example 4 of the same U.S. patent applicationSer. No. 08/672,617, now U.S. Pat. No. 5,780,528 (issued Jul. 14, 1998);230 grams of Witco S-180 stearyl stearamide wax¹, and 275 grams ofPolywax PE850². The materials were melted for 2 hours at 125° C., thenblended by stirring in a temperature controlled mantle for 2 hours at125° C. The ink was then filtered through a heated (125° C.) Mottapparatus (available from Mott Mettalurgical) using a 2μ filter at 5psi. The hybrid ink was poured into molds and allowed to solidify toform ink sticks. This final yellow ink product was characterized by thefollowing physical properties: viscosity of about 12.2 cPs at 140° C. asmeasured by a Ferranti-Shirley cone-plate viscometer, two melting pointsat about 91° C. and about 105° C. as measured by differential scanningcalorimetry using a DuPont 2100 calorimeter and a Tg of about 21 ° C. asmeasured by Dynamic Mechanical Analysis using a Rheometrics SolidsAnalyzer (RSAII). The spectral strength of this ink was not measured.This ink was placed in a Phaser® 340 printer which uses an offsettransfer printing process. The ink was printed using a print headtemperature of 140° C., a drum temperature of 64° C. and a paper preheattemperature of 61° C. The finished prints were found to have acoefficient of friction against glass that varied from about 0.6-1.8 asmeasured by a Thwing-Albert Friction/Peel Tester (Model 225-1). Theirperformance in photocopiers was comparable to the prints from Example 33above. The finished prints were also found to have a resistance toflaking of the ink when folded very similar to the prints made from theink in Example 33 and good scratch resistance.

EXAMPLE 35 Yellow Hybrid Ink Made From a One-Pot Colored Resin Synthesis

In a stainless steel beaker were combined 420 grams of the molten yellowcolored reaction mixture from Example 6, and 150 grams of molten PolywaxPE850¹ (S-180 amide wax² was already in the yellow reaction mixturesince it was used as a solvent for the reaction). The materials wereblended by stirring in a temperature controlled mantle for 1/2 hour at125° C. The ink was then filtered through a heated (125° C.) Mottapparatus (available from Mott Mettalurgical) using a 2μ filter at 5psi. The filtered hybrid ink was poured into molds and allowed tosolidify to form ink sticks. This final yellow ink product wascharacterized by the following physical properties: viscosity of about12.0 cPs at 140° C. as measured by a Ferranti-Shirley cone-plateviscometer, two melting points at about 91° C. and about 105° C. asmeasured by differential scanning calorimetry using a DuPont 2100calorimeter and a Tg of about 20° C. as measured by Dynamic MechanicalAnalysis using a Rheometrics Solids Analyzer (RSAII). The spectralstrength of this ink was not measured. This ink was placed in a Phaser®340 printer which uses an offset transfer printing process. The ink wasprinted using a print head temperature of 140° C., a drum temperature of60° C. and a paper preheat temperature of 60° C. The finished printswere found to have a coefficient of friction against glass that variedfrom about 0.5-1.8 as measured by a Thwing-Albert Friction/Peel Tester(Model 225-1). Their performance in photocopiers was comparable to theprints from Example 33 above. The finished prints were also found tohave excellent resistance to flaking of the ink when folded and goodscratch resistance.

EXAMPLE 36 Cyan Polycarbonate-Modified Hbrid Ink Made From a One-PotResin Synthesis and Powdered Cyan Dye

In a stainless steel beaker were combined 225 grams of the clearreaction mixture from Example 11, 169 grams of Witco S-180 stearylstearamide¹ and 106 grams of Polywax PE850². The materials were meltedtogether at a temperature of about 135° C. in an oven, then blended bystirring in a temperature controlled mantle for 1/2 hr. at 125° C. Tothe clear ink base was added 11.0 grams of Solvent Blue 44, and theresulting mixture was stirred at 125° C. for an additional 2 hours. Theink was then filtered through a heated (125° C.) Mott apparatus(available from Mott Mettalurgical) using a 2μ filter at 5 psi. Thefiltered modified hybrid ink was poured into molds and allowed tosolidify to form ink sticks. This final cyan ink product wascharacterized by the following physical properties: viscosity of about13.1 cPs at 140° C. as measured by a Ferranti-Shirley cone-plateviscometer, two melting points at about 88° C. and about 100° C. asmeasured by differential scanning calorimetry using a DuPont 2100calorimeter and a Tg of about 33° C. as measured by Dynamic MechanicalAnalysis using a Rheometrics Solids Analyzer (RSAII). The spectralstrength of this ink was not measured. This ink was placed in a Phaser®340 printer which uses an offset transfer printing process. The ink wasprinted using a print head temperature of 140° C., a drum temperature of60° C. and a paper preheat temperature of 60° C. The finished printswere found to have a coefficient of friction against glass that variedfrom about 0.6-2.0 as measured by a Thwing-Albert Friction/Peel Tester(Model 225-1). Their performance in photocopiers was comparable to theprints from Example 33 above. The finished prints were also found tohave excellent resistance to flaking of the ink when folded and verygood scratch resistance.

EXAMPLE 37 Yellow Polycarbonate-Modified Hybrid Ink Made From a One-PotPolycarbonate-Modified Colored Resin

In a stainless steel beaker were combined 225 grams of the yellowreaction mixture from Example 8, 137.5 grams of Witco S-180 stearylstearamide¹ and 137.5 grams of molten Polywax PE850². The materials weremelted together at a temperature of about 135° C. in an oven, thenblended by stirring in a temperature controlled mantle for 1 hr. at 125°C. The ink was then filtered through a heated (125° C.) Mott apparatus(available from Mott Mettalurgical) using a 2μ filter at 5 psi. Thefiltered modified hybrid ink was poured into molds and allowed tosolidify to form ink sticks. This final yellow ink product wascharacterized by the following physical properties: viscosity of about13.1 cPs at 140° C. as measured by a Ferranti-Shirley cone-plateviscometer, two melting points at about 88° C. and about 100° C. asmeasured by differential scanning calorimetry using a DuPont 2100calorimeter and two Tgs of about 2° C. and about 30° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).The spectral strength of this ink was not measured. This ink was placedin a Phaser® 340 printer which uses an offset transfer printing process.The ink was printed using a print head temperature of 140° C., a drumtemperature of 62.5° C. and a paper preheat temperature of 60° C. Thefinished prints were found to have a coefficient of friction againstglass that varied from about 0.5-1.1 as measured by a Thwing-AlbertFriction/Peel Tester (Model 225-1). Their performance in photocopierswas comparable to the prints from Example 33 above. The finished printswere also found to have excellent resistance to flaking of the ink whenfolded and very good scratch resistance .

EXAMPLE 38 Cyan "Unithox"-Modified Hybrid Ink Made From a One-Pot"Unithox"-Modified Colored Resin

In a stainless steel beaker were combined 250 grams of the cyan reactionmixture from Example 15, 153 grams of Witco S-180 stearyl stearamide¹and 153 grams of Polywax PE850². The materials were melted together at atemperature of about 120° C. in an oven, then blended by stirring in atemperature controlled mantle for 1 hr. at 125° C. The ink was thenfiltered through a heated (125° C.) Mott apparatus (available from MottMettalurgical) using a 2μ filter at 5 psi. The filtered modified hybridink was poured into molds and allowed to solidify to form ink sticks.This final cyan ink product was characterized by the following physicalproperties: viscosity of about 11.1 cPs at 140° C. as measured by aFerranti-Shirley cone-plate viscometer, two melting points of about 88°C. and about 100° C. as measured by differential scanning calorimetryusing a DuPont 2100 calorimeter and a Tg of about 33° C. as measured byDynamic Mechanical Analysis using a Rheometrics Solids Analyzer (RSAII).The spectral strength of this ink was not measured. This ink was placedin a Phaser® 340 printer which uses an offset transfer printing process.The ink was printed using a print head temperature of 140° C., a drumtemperature of 65° C. and a paper preheat temperature of 60° C. Thecoefficient of friction of the finished prints was not measured.However, their performance in photocopiers was comparable to the printsfrom Example 33 above. The finished prints were also found to have goodresistance to flaking of the ink when folded and very good scratchresistance.

EXAMPLE 39 Yellow "Isofol"-Modified Hybrid Ink Made From a One-Pot"Isofol"-Modified Colored Resin

In a stainless steel beaker were combined 200 grams of the yellowreaction mixture from Example 21, 122 grams of Witco S-180 stearylstearamidel and 122 grams of Polywax PE850². The materials were meltedtogether at a temperature of about 120° C. in an oven, then blended bystirring in a temperature controlled mantle for 2 hr. at 125° C. The inkwas then filtered through a heated (125° C.) Mott apparatus (availablefrom Mott Mettalurgical) using a 2μ filter at 5 psi. The filteredmodified hybrid ink was poured into molds and allowed to solidify toform ink sticks. This final yellow ink product was characterized by thefollowing physical properties: viscosity of about 10.8 cPs at 140° C. asmeasured by a Ferranti-Shirley cone-plate viscometer, two melting pointsof about 88° C. and about 100° C. as measured by differential scanningcalorimetry using a DuPont 2100 calorimeter and a Tg of about 4.1° C. asmeasured by Dynamic Mechanical Analysis using a Rheometrics SolidsAnalyzer (RSAII). The spectral strength of this ink was not measured.This ink was placed in a Phaser® 340 printer which uses an offsettransfer printing process. The ink was printed using a print headtemperature of 140° C., a drum temperature of 60° C. and a paper preheattemperature of 60° C. The coefficient of friction of the finished printswas not measured. However, their performance in photocopiers wascomparable to the prints from Example 33 above. The finished prints werealso found to have good resistance to flaking of the ink when folded andvery good scratch resistance.

The phase change ink composition of the present invention can have apercentage composition of about 0% to about 75% by weight colored resin,about 0% to about 75% by weight colorless resin, and about 25% to about75% by weight combined waxes. A more preferred range is about 0% toabout 50% by weight colored resin, about 0% to about 50% by weightcolorless resin, and about 25% to about 75% by weight combined waxes. Amost preferred range is about 0% to about 40% by weight colored resin,about 0% to about 40% by weight colorless resin, and about 40% to about60% by weight combined waxes.

While the invention has been described above with reference to specificembodiments thereof, it is apparent that many changes, modifications andvariations can be made without departing from the inventive conceptdisclosed herein. For example, it should be noted where a urethanereaction product is obtained, a single alcohol precursor or multiplealcohol precursors may be used with an appropriate isocyanate as long asthe required stoichiometric ratio is maintained. Where a urethane/ureareaction product is obtained, single or multiple alcohol and amineprecursors may be employed within the appropriate stoichiometric ratios.Accordingly, it is intended to embrace all such changes, modificationsand variations that fall within the spirit and broad scope of theappended claims. All patent applications, patents and other publicationscited herein are incorporated by reference in their entirety.

What is claimed is:
 1. A phase change ink composition comprising:(a) afirst urethane resin that is the reaction product of at least onealcohol and an isocyanate, the alcohol being a straight chainedmonohydric aliphatic alcohol of carbon chain length 20 or higher; and(b) a second urethane resin that is the reaction product of at least onestraight chained monohydric aliphatic alcohol of carbon chain length 20or higher, an isocyanate, and at least one chromogen-containingnucleophile.
 2. The phase change ink composition of claim 1 furthercomprising the isocyanate in the first urethane resin and the secondurethane resin being selected from the group consisting of amonoisocyanate, a diisocyanate, a triisocyanate, a copolymer of adiisocyanate, and a copolymer of a triisocyanate.
 3. The phase changeink composition of claim 2 further comprising the isocyanate in thefirst urethane resin being isophorone diisocyanate.
 4. The phase changeink composition of claim 1 further comprising an anti-oxidant.
 5. Thephase change ink composition of claim 1 wherein the first urethane resincomprises from about 5 to about 50% by weight, the second urethane resincomprises from about 5 to about 50% by weight, and the at least onepolyethylene wax comprises about 30 to about 80% by weight.
 6. The phasechange ink composition of claim 1 wherein the first urethane resincomprises from about 10 to about 40% by weight, the second urethaneresin comprises from about 10 to about 40% by weight, and the at leastone polyethylene wax comprises about 35 to about 70% by weight.
 7. Thephase change ink composition of claim 6 wherein the first urethane resincomprises from about 15 to about 30% by weight, the second urethaneresin comprises from about 15 to about 30% by weight, and the at leastone polyethylene wax comprises about 40 to about 65% by weight.
 8. Thephase change ink of claim 1 further comprising a polyethylene wax.